Azo dyestuff



Patented July 28, 1953 AZO DYESTUFF" Robert Lantz. and Georges Mingass-on, Paris,'. France, assignors to Compagnie Francoise des Matieres Colorantes, Saint-Denis, France, a

corporation. of'France No.-Drawing.- Application April? 4,1951, Serial No. 219,317. In France August 24, 1945 Section- 1, Public Law 690, AuguS'tS} 1946 Patent expires August 2,4; 1965 3" Claims; 1

The present application is. a continuation-inpart of our patent application.- Serial Number 741,429,.filed1April 14,1957.

Our invention relates to metalli'zable azo-dyestuiism One object. of our invention is to provide. azodyestufis which are. soluble insodi'um sulfide and are of great importance for dyeing. cellulosic. fibres.

Another object. ofv the invention is. to provide metallizable azo-dyestuff's. which. after being. ap pli'edt on cellulosic. fibres in. a. sulfide bath are capable of. acquiring remarkable fast'nesses when treatedv with. combinations. i heavy metals such as copper..

According to our invention. a benzenic orthoaminophenol substituted on the. benzenic nucleus byv a mercapto. groupie di'azotizedj and the so obtained. diazol-compound. is coupled-1 with. a. cou.- pling component containing an hydroxy group, coupling. in a. position adjacent. that. of said. hydroxy group,- the. coupling component. and the diam-compound. having, no, solublilizing. groups other than hydroxy. grouper The, so, obtained azoeclyestufis have the. following general formula:

in which. represents: a. benzenicr. nucleus subs-ti tuted by a hydroxy group in ortho position-With respect to the azo-group,.and B is the radical of a coupling component containing an hydroxy group, coupling; a position adjacent that of said; hydroxy group; A. and BE containing; no sol ubilizing groups-1 othe'n' than: hydroxy groups;-

The benzenic: nucleus:- repres'ented a by. A may. contain other substituentsbeside: the; 0H.' and -SI-! groups, except. howevenc. as; above stated;- it must-'1 not: contain. groups which; confen solubility in water; nor groups-whichimay be/ -reducediin': the dyeing sodium sulfidebath; permissiblmsubstituentscomprise;. more; particularly,, alkylgroupsandhalogenatoms The diazotization and: coupling are: carried out ,in-the usual manner.. It is sometimes of advantageto. accelerate the couplingreaction adding. a solvent such aspyridin.=.

When. using. the: current. coupling compounds it: is: possible. to, obtain a very extended range: of hues Withthe same diazo; Thus, withamino lhydroxy-3-thiophenol or. with one of the. derivativesof. saidcompound chlorinated in positions. 6 or. -2-6,. colours are obtained. suchas yellow, garnet red,- black, etc.

The ortho-aaninophenols. thev benzenic nucleus. oiwhich is substituted by amercaptogrouprwhichl may; be. usedfor carrying outthepresentinvention-v are,- for example amino-- l'r-hydroxy.li-thicphenoL, amino-3ehydroxyl-thiophenol chloro- 6 amino 4 hydroxy 3 thiophenol, dichloro- 2,6 amino 4- nyerew v 3 thiophenol and aniinolehydroxy-3 metnyle2-thiophenolc Said ortho-aminophenolsare new compounds; They may be obtained; for example, by treating chlorcenitrophenols in which the. chlorine: atom is in para position and the hydroxy group inonthopositien with respect to the. nitro group with a solublesaltofhydrosul furic acid-01: by reducing; ortho-nitrophenols substitued by a sulfo' chloride group; p

The dyestuffs prepatedaccording toour in vem tion are soluble in sodium sulfide and theso obtained solutions arecapable oi dyeing. cellulosip fibres; theresulting; dyeings acquire; remarkable fastnesses when the dyed cellulosia fibres aiie treatedwith compounds of heavy metwlsrsuch as copper, for'examplel The following. are: non] limitative examplesil lustrating. our inventiont In said. examples tlie parts are parts by Weight, except; where otheri- Wise indicated.

Example 1 40': parts sodium salt'of' ch1orc-3-nitrc-6 -pnm 1 are. heated for a pence of"7' h"(iuis"so that the condensed" liquid fib'wsback; with mo'pa ts'water and parts crystallized sodium siilfide; The soi'uticnred-brown at" first; takes; on: a slight greenish-brown hue: Aft'erieooiing. a carbon orox'ide' fi'ow'i's' caused. to' pass: through. the sointlbn and 5 parts sodium acetate" are added. as well as hydrochloric; acid? until" the solution: becomes acid toward'sl'lit'nius.

precipitate is obtained, which issoliible' ii'f acids" and'alls'a'lies andaltersrathrfrreadily'intliepis enc'e ofa'ii'.

Example 2" A mixture of 40 parts dich1oro-3-4-nitro-6- phenoly 33 partsof: so sodm lye, 116: parts of crystallized: sodium'isulfide: andifiOO: parts? on watch areaboiled fort? hours in an apparatus provided witna-refiuxcooling devices. After-1 cooling; 10 parts: sodium acetate are added: and: them hydro chlonic: acid untili the: solution. becomes" acid to litmus; 'llhe: resulting precipitate is. filtered; washedawith' Water." and llfa -dlsfilved in: dilute -hy cl'ro'chlbric acid; after filtratiom the' solutionis again". precipitated: by; means of; anaddition on sodium. acetate; The. properties of. the resulting chlbm-d-amincaAehydroiiy 3 thiophenolaare 'sim ilar to those of the substance: prepared accord ing tovExamplell 'Dhe: starting? substance, which; has a} melting; pointmfi 82-8259" (3"; lisaprepared l causing dilute: soda to ant upbm t'richlorm-3=4-51dinitrob1#2 benzene.

Example 3' 8 parts of-l trichloroi-z-e-4-nitro- 6 plenol* are: dissolved in 200 parts of water and 4.5 parts of 30% soda lye. After adding 8 parts of crystallized sodium sulfide, the solution is boiled for a few minutes. Dichloro-2-5-nitro-4-hydroxy-3- thiophenol is then precipitated by means of an addition of hydrochloric acid. The resulting compound, recrystallized from alcohol, melts at 103 C. 12 parts of said compound are dissolved in 200 parts of water and 14 parts of 35% soda lye, and sodium hydrosulfite is then added at low temperature, while stirring, until the solution is discoloured, while maintaining the alkaline pH of the medium. By addition of acetic acid, dichloro '2 6 amino 4 hydroxy 3 thiophenol precipitates, which can be recrystallized from methyl alcohol.

. Example 4 11 parts of amino-4-hydroxy-3-thiophenol obtai'ned' according to the method described in Example 1 are dissolved in 17 parts of 31% hydrochloric acid and 250 parts of water. The obtained solution is cooled down to 5 C. and is added to a solution of 3.5 parts of sodium nitrite in 30 parts of water. The resulting liquid, which contains an orange-brown precipitate of diazocompound, is poured into a solution containing 7.2 parts of beta-naphthol, 200 parts of water and 12 parts of 35% soda lye. When the coupling is ended, the solution is neutralized with hydrochloric acid and a dyestuif precipitates. Saiddyestufi is filtered, washed and dried. It forms a bluish-black powder, yielding at room temperature a blue solution in a sodium sulfide solution. The addition of 50 parts of pyridine to the beta-naphthol solution considerably speeds up the coupling.

Example 5 The amino-4-hydroxy-3-thiophenol obtained, as stated in Example 1, from 195 parts of the sodium salt of chloro-3-nitro-6-phenol is impas'ted in 640 parts of water and dissolved by addition of 1150 parts of 20 B. hydrochloric acid. Theobtained solution is cooled down to 5 C. and is diazotized by addition of a 4.5 N sodium nitrite solution. The obtained diazo suspension is poured into a solution containing 150 parts of phenyl-1-methy1-3-pyrazolone-5, 1200 parts of water, 105 parts of 40 B. soda lye and 91 parts of, sodium carbonate. A dyestuff precipitates, which is filtered, washed and dried. The characteristics of said dyestuff are given in Table I at the end of the present specification.

Eaample 6 -A quantity of moist dichloro-2,6-amino-4-hydroxy-3-thiophenol requiring 5.4 parts of sodium nitrite for diazotization is dissolved in 100 parts of water and 17 parts of 20 B. hydrochloric acid, and diazotized with the above mentioned quantity of sodium nitrite in 20% solution. The'obtained suspension of diazo-compound is poured into a solution containing 11 parts of hydroxy-2naphthalene and 20 parts of 38 B. soda lye. An insoluble dyestufi precipitates, which is filtered. The characteristics of said dyestufi are given in Table III at the end of the present specification.

The dichloro 2,6 amino 4 hydroxy 3- thiophenol used in the present example was obtained according to the procedure of Example 3 but without drying or re-crystallization.

Example 7 A quantity of chloro-6-amino-4-hydroxy-3- thiophenol requiring '7 parts of sodium nitrite for of water.

diazotization is dissolved in 125 parts of water and 25 parts of 20 B. hydrochloric acid and diazotized with the above mentioned quantity of sodium nitrite in 20% solution. The obtained suspension of diazo-compound is poured into a solution containing 16 parts of hydroxy-2-naphthalene, 14 parts of 38 B. soda-lye and 100 parts After an addition of hydrochloric acid the precipitated dyestuff is filtered, washed and dried. Its characteristics are given in Table II at the end of the present specification.

The chloro-G-amino-4-hydroxy-3-thiophenol used for this preparation was obtained according to the procedure of Example 2.

Example 8 A solution of amino-3-hydroxy-4-thiophenol prepared as stated hereinafter is diazotized at a temperature of O-5 C. with 62.5 parts by volume of a solution containing 280 grams of sodium nitrite per litre. A diazo-compound is precipitated, which is filtered and washed with water.

A quantity of said moist precipitate containing 8.85 parts of dry product is added in portions to a solution containing 8 parts of hydroxy-2- naphthalene, 2.3 parts of sodium hydroxide and 60 parts of water. The whole is then stirred for 3 hours at room temperature and for one hour at 40 C. After a rest of 12 hours, 30 parts by volume of a saturated solution of sodium chloride are added, the temperature is brought to C., and the dyestuff obtained is filtered after cooling and washed with water.

The characteristics of the so obtained dyestufi are given in Table IV at the end of the present specification.

The solution of amino-3-hydroxy-4thiophenol used. is obtained by mixing little by little parts of nitro-3-hydroxy-4-benzene sulfochloride and 150 parts of zinc powder in 440 parts by volume of 22 B. hydrochloric acid, without exceeding the temperature of 50 C. The whole is brought to a boil and 50 parts of zinc powder and 30 parts by volume of hydrochloric acid are further added. The obtained liquor is filtered and the filtrate is collected.

Example 9 The quantity of amino-4-hydroxy-3-methyl-2- thiophenol obtained according to the hereinafter given indications is dissolved in parts of water and 11 parts of 20 B. hydrochloric acid. To the obtained solution cooled down to 5 C., 27 parts of a 70% solution of sodium nitrite are added. A precipitate of diazo derivative is formed which is filtered and then coupled with a solution containing 5 parts of beta-naphthol, 100 parts of water and 7 parts of 40 B. soda lye. After coupling, the precipitation of the dyestuff is completed by addition of sodium bicarbonate.

The characteristics of said dyestufi are given in Table V at the end of the present specification.

The amino-4-hydroxy-3-methyl-2-thiophenol used for the above preparation is obtained in the following manner: chloro-2-dinitro-5-6-methylbenzene is hydrolyzed by means of sodium hydroxide and 10 parts of the obtained sodium salt of nitro 4 hydroxy 3 methyl 2 chloro-- acid to litmus paper. A yellow-brown precipi- "tate of amino=4.-hydroxy-;3=methyle21thiophenol isseparated by filtration.

Example 6.5 partof the dyestuff obtained in Example 4 is disselvedin 2.5. parts of an aqueous solution containing 1 part of crystallized sodium sulfide and the resulting solution is poured into a solution of parts of crystallized sodium sulfate and 150 parts .of water. 10 parts of cotton yarn are dyed for one hour at room temperature in the thus obtained mixture and are then rinsed. The fibre is dyed a marineblue turning to red under the action 915 wide.

Fibres or objects made of natural or regene elat d c llulo u h for instance, ray n il fibr r cellophane, a e died in t e ame. manner, by using the same dyestuff or other dyestuf s prepared according to the invention.

Example 11 T e fibres dyed according to he p eced ng examples are immersed for one quarter of an hour, at room temperature, in a bath of parts of water containing 0.2 part of copper sulfate and, either 0.3 part of acetic acid, asufiioient amount of ammonium hydroxide for obtaining a homogeneous solution, or 0.25 part tartaric acid and the necessary amount of sodium hydroxide for neutralizing the solution. A purple hue is obtained having excellent fastnesses, more particularly to washing and .mli llt.

The same method may be applied to other ob-- jects made of cellulose or to other dyestuffs prepared accord n o the invention I Thefollowing Tables I,v IIand .III give. the characteristics of dyestuffs obtained when starting ire diazotized amino-ebrdroxsz-BT-thionhenol. hloro -am no--h dro y-3-thiop o1 and dichloro-Z.(i-aminoi-hydroxy-3-thiopheno1 respectively, and coupling said compounds with various coupling compounds. Tables IV and V g-iue .the ch act ri ics of he dyestu s. ehtainedacco dine to the above Example .8. anti 9 espectively.

TABLE I Solution in con- Am1no-4-hydroxy -3-tlnophenol Solution in so- Direct dyeing Cop cred d ewithcentr-ated-sul' dium sulfide on cotton ing )11 cottgn iuric 801d HydroXy-2-naptha1ene bluish-purple". purple blue purple. Acetylacetanilide reddish-brown reddish-y reddish-yellow" brown-yellow, Acetylacetometaxylidide do do. do D Di(acetylacetamino)-4-.4-dim et h y ldo red yellow.

3.3-diphenyl. Phenyl-l-methyl-B-pyrazolone-5 red do r d reddish-brown, Hydroxy-3-phenylamino-benzenepurplereddish-purple purple-brown. Di-hydroxy-Z-fi-napthalene ue... greenisb-blue.. purplish-blue, Di-hydroxy-2-7-napthalone do blue purple. Dl-hydroxy-l-5-naphthalene.. greenish-blue. purple blue-grey. Di-hydroxy-l-s-napth alene do purplish-red. black-grey. Hydroxy-5-amino-1- n a p h th ale n e blue do Do.

(alkaline coupling).

TABLE II Solution in con- ChlOIO-(i-QH]1I10-4-hyd1OXy-3- Solution in Direct dyeing Ooppered dyeing thiophenol withcentratgggulmne sodium sulfide on cotton on cotton H droxy-Q-naphthalene purple purple. Aget lacetanilide reddish-brown yellowish-brown. Pbenyl-l-methyl-3-pyrazo1one-5 brownish-red do reddish-brown. Di (acetylacetamino) 4.4dimethyl-3.3- reddish-brown. do ye1l0w diphenyl.

Hydroxy-S-phenylamino-benzene purple reddish-purple" purple b wn, Dihydroxy-2.6-naphthalene ue blue b1 purplish-blue, Di-hydroxy-2.7-naphthalene. do purple. Di-hydroxy-1.5-naphthalene. greenish-blue black-grey Di-hydroxy-LS-naphthalene d0 D Hydroxy-fi-amino-l-naphthalene (alkablue Do.

line coupling).

TABLE III v Solution in con- D1chl0r0-2.6-ammo'4'h drox -3-th1ophenol Solutionmsodium Direct dyeing Ooppered dyewith y centragfigulmm sulfide on cotton ing on cotton Hydroxy-2-naphthalene purple purplish-blue purple. Hydroxy-2-naphthoyl-3-aminobenzene .do blue Do. (Hydroxy-2-naphthoyl-3-amino) l-methyl-Z- purple red purpllsh-blue Do.

benzene. (Hydroxy-2-naphthoyl-3-amino)l-methoxydo do do Do.

2-benzene. (Hydroxy-2-naphthoyl-3-a1nino) Z-naphthagreyish-blue do purple Do.

lene. (Hydroxy-2-anthraquinoyl-3-amino) lgreenish-blue... blue green-blue green.

methyl-2-benzene. (Di-acetylacctamino)4.4-dimethyl-3.3- brown-yellow reddish-brown orange-red orange-yellow.

diphenyl. Di-hydroxy-l.5-napl1thalene greemsh-blue blue bl e grey. Di-hydroxy-2.6-naphthalene blue do purple. Di-hydroxy-2.7-naphthalene purp11sh-blue purplish-red. Do. Di-hydroxy-ls-naphthalene greenish-blue purple-red. brown. Hydroxy-5-amino-l-naphthalene(alka1i.ue Black-blue blue brown-grey.

coupling). Resorcinol l. red red purple bordeaux. Phenyl-l-methyl-3-pyrezolone-5 brown-red. yellowish-brown orange-yellow.-. red brown. Acetylacetanilide orange red orange-yellow. Hydr0xy-3-phenylaminobenzene". black-blue purplish-brown. brown-purple. Chloro-4-hydroxy-1-naphthalene blue p black-blue purplish-blue. Ohloro-3-hydroxy-2-naphthelene do purpllsh-red blue purple.

TABLE IV Solution irect Goppered Amino-3-hydroxy-4- g soludt-lonm dyeing dyeing thiophenol withffi i 1 23 on on 5 acid cotton cotton Madroxy-Z-naphthavioiet violet-blue. violet... violet.

ene.

, TABLE V Solution 7 Amino-4-hydroxy-3-in concen- Solutionin 5 235 g gg melthygl-f-thiophe 1 w; soggiim 1 g no Wi s [1110 s e acid cotton cotton Beta-naphthol blue vigllaeeous violet... violet.

ue. I

lowing general structural formula:

8 in which B is the radical of a coupling component the coupling position of which is adjacent'that of a hydroxyl group and which contains no solubilizing group other than hydroxyl groups.

2. An azodyestuff according to claim 1 in which B is the radical of an hydroxylated derivative of naphthalene.

3. An azodyestufi according to claim 1 in which B is the 2-hydroxy naphthalene radical.

ROBERT LANTZ. GEORGES MINGASSON.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A METALLIZABLE AZODYESTUFF HAVING THE FOLLOWING GENERAL STRUCTURAL FORMULA: 